Field of the Invention
This invention relates to antioxidants which contain nitrogen, sulfur and optionally oxygen atoms. The compositions are particularly useful in lubricant compositions for their antioxidant ability. In U.S. Pat. No. 2,282,710 to Dietrich issued May 12, 1942 it is known that stabilization of petroleum hydrocarbons against the deleterious catalytic action of metals may be obtained by compositions containing both a nitrogen and a sulfur functional group. Various cyclic, aromatic and linear carbon configurations are shown in the sulfur and nitrogen containing molecules of Dietrich. Dietrich discloses preparing his compositions by the use of ethylenimine. Dietrich further states that his compounds are particularly effective in retarding the formation of products corrosive to metals, and particularly cadmium, silver, copper, lead and like bearing alloys under normal service conditions.
German OLS No. 1,066,019 published Sept. 24, 1959 by Holtschmitt et al describes various condensation products of thioglycol and nitrogen containing materials. Holtschmitt shows his compounds as containing free hydroxyl groups. Holtschmitt further discloses the use of aromatic amines containing a short aliphatic group on the aromatic ring, e.g. toluidine.
It is known from an article entitled Thioglycol Polymers I Hydrochloric Acid-Catalysed Auto Condensation of Thiodiglycol by Woodward, Journal of Polymer Science the OL XLI, Pages 219-223 (1959), that the properties of a sulfur and oxygen containing compound allow end-to-end condensation. It is further known from the Woodward article that multiple sulfur linkages within the molecule, e.g. disulfides, trisulfides, and the like may be obtained.
It is further known that various amines may be utilized in antioxidant compositions. Phenothiazine compounds are known in lubricant products from U.S. Pat. No. 2,781,318 issued Feb. 12, 1957 to Cyphers. The alkyl phenothiazines of Cyphers are alkylated on the phenylene rings of the phenothiazine structure. Cyphers does not show or suggest the alkylation of the amine nitrogen in phenothiazine. The Cyphers patent is directed to the utility of phenothiazine as an antioxidant and corrosion inhibiting additive for ester, polyester, polyether and other synthetic lubricants.
U.S. Pat. No. 3,536,706 issued Oct. 27, 1970 to Randell suggests that phenothiazines may be used as additives for synthetic lubricants. The phenothiazines particularly described by Randell are those containing tertiary alkyl substituents having from 4 to 12 carbon atoms on the aryl groups which make up the phenothiazine structure. Randell also discloses fused rings on the two phenylene groups which make up the phenothiazine structure. Stated otherwise, Randell allows the utilization of naphthalene for at least one of the two aryl groups in the phenothiazine structure.
U.S. Pat. No. 3,803,140 issued to Cook et al on Apr. 9, 1974 describes various tertiary alkyl derivatives of phenothiazine. N-alkyl substitution or N-alkenyl substitution is described on the phenothiazine structure. Ring alkylation when the phenothiazine is in the free nitrogen form is also shown. Cook et al express a preference for non-N substituted phenothiazine derivatives.
Cook et al also suggest that organic materials which are susceptible to oxidative degradation may benefit through the use of the compounds of their invention. Such uses include antioxidants for aliphatic hydrocarbons such as gasoline, lubricating oils, lubricating greases, mineral oils, waxes, natural and synthetic polymers such as rubber, vinyl, vinylidene, ethers, esters, amides and urethanes. The compounds of Cook et al are also suggested for stabilizing aldehydes and unsaturated fatty acids or esters thereof. Still further utilities suggested by Cook et al include the stabilization of organo-metalloid substances such as silicone polymers. Another class of uses of the compounds of Cook et al include the stabilization of vitamins, essential oils, ketones and ethers.
Normant in U.S. Pat. No. 3,560,531 issued Feb. 2, 1971, describes metallation of materials having active hydrogens including phenothiazine. U.S. Pat. No. 3,344,068 issued Sept. 26, 1967, to Waight et al describes antioxidants for ester-based lubricants. Waight et al's compounds have an N-hydrocarbyl substituted phenothiazine structure. The N-substituted phenothiazine compounds of Waight et al are also substituted in at least one position on the fused aromatic nuclei. A second required component in the compositions of Waight et al is a secondary aromatic amine having two aromatic groups attached to the nitrogen atom.
The preparation of alkylthioalkanols which are useful as intermediates for preparing the compounds of the present invention are described in U.S. Pat. No. 4,031,023 to Musser et al. The Musser et al patent was issued June 21, 1977 and is assigned to The Lubrizol Corporation.
U.S. Pat. No. 2,994,527 to Winthrop et al which issued Nov. 24, 1959, describes pharmaceutical compounds such as omega-(10-phenothiazinyl)alkyl di-alkyl sulfonium salts which are useful as spasmolytics and in particular antihistaminics. U.S. Pat. No. 3,376,224 issued Apr. 2, 1968 to Elliott et al describes phenothiazine derivatives which are stated to be N-substituted methylene compounds which contain an ether linkage between the methylene group and an alkyl or cycloalkyl radical. According to Elliot et al, the alkyl or cycloalkyl radical may carry an alkoxy or other non-reactive substituent.
It has been found in the present invention that particularly effective antioxidant compositions may be obtained through the inclusion of a nitrogen functionality from an amine, and an oxygen and sulfur functionality from a compound such as a beta-thiodialkanol. Of course, within the present invention other methods of preparing the claimed compounds will be apparent.
Throughout the specification and claims percentages and ratios are by weight, temperatures are in .degree.C., and pressures are in KPa gauge unless otherwise indicated. To the extent that the references cited herein are applicable, they are incorporated by reference.